EP0150832A2 - Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung - Google Patents

Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung Download PDF

Info

Publication number
EP0150832A2
EP0150832A2 EP85100784A EP85100784A EP0150832A2 EP 0150832 A2 EP0150832 A2 EP 0150832A2 EP 85100784 A EP85100784 A EP 85100784A EP 85100784 A EP85100784 A EP 85100784A EP 0150832 A2 EP0150832 A2 EP 0150832A2
Authority
EP
European Patent Office
Prior art keywords
catalyst
zirconium oxide
terminal
compound
selectivity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85100784A
Other languages
English (en)
French (fr)
Other versions
EP0150832A3 (en
EP0150832B1 (de
Inventor
Masashi Araki
Kazuteru Takahashi
Takuo Hibi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP59013920A external-priority patent/JPS60158121A/ja
Priority claimed from JP59177217A external-priority patent/JPS6153230A/ja
Priority claimed from JP59252298A external-priority patent/JPS61130240A/ja
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of EP0150832A2 publication Critical patent/EP0150832A2/de
Publication of EP0150832A3 publication Critical patent/EP0150832A3/en
Application granted granted Critical
Publication of EP0150832B1 publication Critical patent/EP0150832B1/de
Expired legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof

Definitions

  • the present invention relates to a method for producing a compound having a double bond at the terminal (hereinafter referred to as terminal olefin). More particularly, the present invention relates to a method for producing the terminal olefin by dehydration of a compound represented by the formula (I), wherein R is a C 3 - c 20 hydrocarbon group which may have one or more double bonds.
  • an olefin can be produced by dehydration of a compound represented by the formula (I).
  • the details of the method can be known, for example, from J. Am. Chem. Soc., 85, 2180 (1963), Oil Chemistry, 17, 236 (1968), etc.
  • Thorium oxide is known as a catalyst for the selective production of the terminal olefin, but its use in industry is difficult because thorium is a radioactive element so that there occurs a serious problem of safety in handling thorium oxide as a catalyst.
  • the present inventors extensively studied to overcome the defects of the conventionally well-known catalyst, i.e.,
  • An object of the present invention is to provide a method for producing terminal olefinsat low costs and with safety which is useful as a material for heat-resistant polymers, a comonomer for polyolefins, a raw material for detergents and the like.
  • the accompanying drawing shows the relationship between the total content of silicon dioxide and titanium dioxide and the selectivity of vinylcyclohexane.
  • the starting material used in the method of the present invention is a compound represented by the formula (I), wherein R is a C 3 - C 20 hydrocarbon group which may have one or more double bonds.
  • R is not particularly limited so far as it is a C 3 - C 20 hydrocarbon group, but it is preferably a C 3 - C 10 hydrocarbon group and more preferably a C 3 -C 10 saturated hydrocarbon group.
  • 4-methyl-2-pentanol and 1-cyclohexylethanol are most preferred.
  • the OH group and the hydrogen atom of the methyl group in the formula (I) are released in the form of water to selectively produce the terminal olefin.
  • zirconium compounds are produced by various methods using Zircon, Baddeleyite, etc. as a raw material, but complete removal of silicon, titanium, aluminum, iron, etc. contained in raw ores is so difficult that it is usual for zircornium products to contain these impurities in trace amounts.
  • the zirconium oxide used in the present invention is of high purity, and that it does not contain particularly silicon and titanium among these impurities so far as possible.
  • the total content, as oxide, of the both metals is 0.3 wt.% or less, a sufficient selectivity is obtained in the production of the terminal olefin, and when the total content is 0.1 wt.% or less, a more preferred selectivity is obtained.
  • Zirconium oxide used in the present invention is obtained by various methods, and particularly, one obtained by calcination of zirconium compounds at 300° to 1500°C is preferred.
  • preferred examples of zirconium compound used for calcination include for example zirconium hydroxide, zirconyl hydroxide, zirconium nitrate, zirconyl nitrate, zirconyl carbonate, zirconium alkoxide and the like. These compounds may be calcined in a state wherein they are supported on suitable carriers, or zirconium oxide after calcination may be supported on suitable carriers.
  • zirconium oxide itself after calcination as a catalyst without using carriers. It is also possible to prepare the catalyst in the coexistence of a second component such as yttrium, etc. if necessary.
  • the calcination temperature is generally 300° to 1500°C, but preferably, a temperature of 500° to 1100°C is employed.
  • the calcination time is generally 0.1 to 50 hours, but preferably, a period of time of 1 to 10 hours is employed. Generally, the activity tends to lower as the calcination temperature becomes high, and sufficient activity comes to fail to appear when the temperature exceeds 1500°C.
  • a method of reaction is not particularly limited, but generally, a gas-phase reaction of fixed-bed form or fluidized-bed form is employed.
  • the reaction temperature is generally 200° to 500°C, but preferably, a temperature of 300° to 400°C is employed.
  • the reaction pressure is not particularly limited, and the reaction may be carried out at atmospheric pressure or under pressure a little higher than that. If necessary, a method may also be employed in which the starting material (I) is reacted in dilution with an inert gas such as nitrogen, etc. The reaction under a reduced pressure also gives a good result.
  • a rate of 0.1 to 15 hr -1 preferably 0.5 to 5 hr as expressed by LHSV, is employed.
  • a hard glass tubular reactor of 12.5 mm in internal diameter having at the center a tubular sheath of.4 mm in external diameter for temperature measurement was packed with 12 ml of a zirconia catalyst, which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7nm at 1000°C for 2 hours, and externally heated in an electric furnace.
  • a zirconia catalyst which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7nm at 1000°C for 2 hours, and externally heated in an electric furnace.
  • the reaction gas from the tubular reactor was analyzed by gas chromatography.
  • Example 1 Experiments with various kinds of alcohol were carried out in the same manner as in Example 1 except that the amount of catalyst used was 4 ml; the alcohol, a starting material, was supplied together with 0.4 1/min of nitrogen gas; and the zirconium oxide catalyst used was prepared by calcining zirconyl nitrate [ZrO(NO 3 )2 2H 2 0] at 1000°C for 2 hours, and its Sio 2 and TiO 2 contents were 0.05 wt.% or less and 0.01 wt.% or less, respectively. The results are shown in Table 1.
  • a hard glass tubular reactor of 19 mm in internal diameter having at the center a tubular sheath of 6 mm in external diameter for temperature measurement was packed with 27 ml of a zirconia catalyst, which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 1000°C for 2 hours, and externally heated in an electric furnace.
  • a zirconia catalyst which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 1000°C for 2 hours, and externally heated in an electric furnace.
  • the reaction gas from the tubular reactor was trapped and analyzed by gas chromatography.
  • a stainless steel tubular reactor of 16 mm in internal diameter having at the center a tubular sheath of 4 mm in external diameter for temperature measurement was packed with 30 ml of zirconium oxide having a particle size of 0,7 to 1,7 mm and externally heated in an electric furnace.
  • the reaction gas from the reactor was trapped and analyzed by gas chromatography.
  • a stainless steel tubular reactor of 4 mm in internal diameter was packed with 7.4 ml of a zirconia catalyst prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 500°C for 2 hours, and externally heated in an electric furnace.
  • a zirconia catalyst prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 500°C for 2 hours, and externally heated in an electric furnace.
  • the reaction gas from the reactor was analyzed by gas chromatography.
  • a stainless steel tubular reactor of 8 mm in internal diameter was packed with 50 ml of a zirconia catalyst which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 400°C for 2 hours, and externally heated in an electric furnace.
  • a zirconia catalyst which had been prepared by calcination of zirconium hydroxide having a particle size of 0,7 to 1,7 mm at 400°C for 2 hours, and externally heated in an electric furnace.
  • the reaction gas from the reactor was analyzed by gas chromatography.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP19850100784 1984-01-27 1985-01-25 Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung Expired EP0150832B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP13920/84 1984-01-27
JP59013920A JPS60158121A (ja) 1984-01-27 1984-01-27 ビニルシクロヘキサンの製造方法
JP177217/84 1984-08-24
JP59177217A JPS6153230A (ja) 1984-08-24 1984-08-24 末端に二重結合を有する化合物の製造方法
JP252298/84 1984-11-28
JP59252298A JPS61130240A (ja) 1984-11-28 1984-11-28 末端に二重結合を有する化合物の製法

Publications (3)

Publication Number Publication Date
EP0150832A2 true EP0150832A2 (de) 1985-08-07
EP0150832A3 EP0150832A3 (en) 1986-03-19
EP0150832B1 EP0150832B1 (de) 1988-11-02

Family

ID=27280453

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19850100784 Expired EP0150832B1 (de) 1984-01-27 1985-01-25 Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung

Country Status (3)

Country Link
EP (1) EP0150832B1 (de)
CA (1) CA1235144A (de)
DE (1) DE3565977D1 (de)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0222356A1 (de) * 1985-11-11 1987-05-20 Sumitomo Chemical Company, Limited Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung
US5057638A (en) * 1990-06-22 1991-10-15 Chevron Research And Technology Company Process for making 1-hexene from 1-butene
US5057636A (en) * 1990-06-22 1991-10-15 Chevron Research And Technology Company Process for recovering N-hexenes from a mixture of C6 olefin isomers by oligomerizing the branched-chain C6 olefin isomers in the mixture using a moderate strength acid catlyst
US5057637A (en) * 1990-06-22 1991-10-15 Chevron Research And Technology Company Process for producing C5 to C18 straight chain α-olefins from the corresponding internal olefins
US5059734A (en) * 1990-06-22 1991-10-22 Chevron Research And Technology Company Process for selectively producing C5 to C18 straight chain α olefins
US5059733A (en) * 1990-06-22 1991-10-22 Chevron Research And Technology Company Process for making 1-hexene and high octane blending components
US5130287A (en) * 1990-06-22 1992-07-14 Chevron Research And Technology Company Method of making a hydrous zirconium oxide dehydration catalyst and product prepared by the method
WO2001044145A1 (en) * 1999-12-14 2001-06-21 Fortum Oil And Gas Oy Method for the manufacture of olefins
KR100688797B1 (ko) 2003-12-15 2007-02-28 에스케이 주식회사 2차 알코올의 탈수반응에 의한 알파-올레핀의 제조방법
WO2012016787A1 (en) 2010-08-03 2012-02-09 Total Petrochemicals Research Feluy Process to make olefins from isobutanol
WO2012016785A1 (en) 2010-08-03 2012-02-09 Total Petrochemicals Research Feluy Combined process to make olefins from isobutanol
WO2012016786A1 (en) 2010-08-03 2012-02-09 Total Petrochemicals Research Feluy Process to make olefins from isobutanol
CN103333038A (zh) * 2013-07-19 2013-10-02 沈阳市宏城精细化工厂 一种生产长碳链α线性烯烃的方法
US9469575B2 (en) 2011-12-15 2016-10-18 Dow Global Technologies Llc Non-reductive dehydroxylation of vicinal compounds to olefins using a halogen-based catalyst
US9968914B2 (en) 2012-12-26 2018-05-15 Kao Corporation Method for producing olefin
WO2023214014A1 (fr) 2022-05-06 2023-11-09 Totalenergies Onetech Procédé de fabrication d'un carburéacteur comprenant une étape de conversion d'un flux d'alcool dans un lit fluidisé, carburéacteur et installation associés
WO2023214001A1 (fr) 2022-05-06 2023-11-09 Totalenergies Onetech Procédé d'obtention d'hydrocarbures, et installation associée
WO2023214015A1 (fr) 2022-05-06 2023-11-09 Totalenergies Onetech Procédé de fabrication d'un carburéacteur, carburéacteur et installation associés

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011084550A (ja) * 2009-09-17 2011-04-28 Sumitomo Chemical Co Ltd 二重結合を有する化合物の製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH421077A (fr) * 1962-12-20 1966-09-30 Continental Oil Co Procédé de production d'alpha-oléfines par déshydratation d'alcools secondaires
US4490567A (en) * 1982-04-08 1984-12-25 Phillips Petroleum Company Catalyst and process for dehydrating 2-alcohols

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH421077A (fr) * 1962-12-20 1966-09-30 Continental Oil Co Procédé de production d'alpha-oléfines par déshydratation d'alcools secondaires
US4490567A (en) * 1982-04-08 1984-12-25 Phillips Petroleum Company Catalyst and process for dehydrating 2-alcohols

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 85, 1963, Easton A.J. LUNDEEN et al. "Selective catalytic dehydration of 2-alcohols; a new synthesis of 1-olefins" pages 2180-2181 *

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0222356A1 (de) * 1985-11-11 1987-05-20 Sumitomo Chemical Company, Limited Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung
US5059734A (en) * 1990-06-22 1991-10-22 Chevron Research And Technology Company Process for selectively producing C5 to C18 straight chain α olefins
US5057637A (en) * 1990-06-22 1991-10-15 Chevron Research And Technology Company Process for producing C5 to C18 straight chain α-olefins from the corresponding internal olefins
US5057638A (en) * 1990-06-22 1991-10-15 Chevron Research And Technology Company Process for making 1-hexene from 1-butene
US5059733A (en) * 1990-06-22 1991-10-22 Chevron Research And Technology Company Process for making 1-hexene and high octane blending components
US5130287A (en) * 1990-06-22 1992-07-14 Chevron Research And Technology Company Method of making a hydrous zirconium oxide dehydration catalyst and product prepared by the method
US5057636A (en) * 1990-06-22 1991-10-15 Chevron Research And Technology Company Process for recovering N-hexenes from a mixture of C6 olefin isomers by oligomerizing the branched-chain C6 olefin isomers in the mixture using a moderate strength acid catlyst
WO2001044145A1 (en) * 1999-12-14 2001-06-21 Fortum Oil And Gas Oy Method for the manufacture of olefins
KR100688797B1 (ko) 2003-12-15 2007-02-28 에스케이 주식회사 2차 알코올의 탈수반응에 의한 알파-올레핀의 제조방법
WO2012016787A1 (en) 2010-08-03 2012-02-09 Total Petrochemicals Research Feluy Process to make olefins from isobutanol
WO2012016785A1 (en) 2010-08-03 2012-02-09 Total Petrochemicals Research Feluy Combined process to make olefins from isobutanol
WO2012016786A1 (en) 2010-08-03 2012-02-09 Total Petrochemicals Research Feluy Process to make olefins from isobutanol
US9056807B2 (en) 2010-08-03 2015-06-16 Total Research & Technology Feluy Process to make olefins from isobutanol
US9056806B2 (en) 2010-08-03 2015-06-16 Total Research & Technology Feluy Process to make olefins from isobutanol
US9079813B2 (en) 2010-08-03 2015-07-14 Total Research & Technology Feluy Process to make propylene from isobutanol by dehydration and subsequent cracking
US9469575B2 (en) 2011-12-15 2016-10-18 Dow Global Technologies Llc Non-reductive dehydroxylation of vicinal compounds to olefins using a halogen-based catalyst
US9968914B2 (en) 2012-12-26 2018-05-15 Kao Corporation Method for producing olefin
CN103333038B (zh) * 2013-07-19 2015-07-15 沈阳市宏城精细化工厂 一种生产长碳链α线性烯烃的方法
CN103333038A (zh) * 2013-07-19 2013-10-02 沈阳市宏城精细化工厂 一种生产长碳链α线性烯烃的方法
WO2023214014A1 (fr) 2022-05-06 2023-11-09 Totalenergies Onetech Procédé de fabrication d'un carburéacteur comprenant une étape de conversion d'un flux d'alcool dans un lit fluidisé, carburéacteur et installation associés
WO2023214001A1 (fr) 2022-05-06 2023-11-09 Totalenergies Onetech Procédé d'obtention d'hydrocarbures, et installation associée
WO2023214015A1 (fr) 2022-05-06 2023-11-09 Totalenergies Onetech Procédé de fabrication d'un carburéacteur, carburéacteur et installation associés
FR3135264A1 (fr) 2022-05-06 2023-11-10 Totalenergies Onetech Procédé de fabrication d’un carburéacteur, carburéacteur et installation associés
FR3135265A1 (fr) 2022-05-06 2023-11-10 Totalenergies Onetech Procédé d’obtention d’hydrocarbures, et installation associée
FR3135263A1 (fr) 2022-05-06 2023-11-10 Totalenergies Onetech Procédé de fabrication d’un carburéacteur comprenant une étape de conversion d’un flux d’alcool dans un lit fluidisé, carburéacteur et installation associés

Also Published As

Publication number Publication date
EP0150832A3 (en) 1986-03-19
CA1235144A (en) 1988-04-12
DE3565977D1 (en) 1988-12-08
EP0150832B1 (de) 1988-11-02

Similar Documents

Publication Publication Date Title
EP0150832B1 (de) Verfahren zur Herstellung von Verbindungen mit endständiger Doppelbindung
CA1211098A (en) Conversion of methane to olefins and hydrogen
EP0498573B1 (de) Verfahren zur Herstellung von Propylene
US4367342A (en) Olefin epoxidation
EP0082641B1 (de) Katalysatoren für die Herstellung von Alkoholen aus Olefinen und Synthesegas und solche Katalysatoren verwendendes Verfahren
EP1473083B1 (de) Verfahren zur Herstellung von aktivierten Methathesekatalysatoren
EP0441430A1 (de) Katalytische Dehydrierung von C2-C5-Paraffinen
EP0434485A1 (de) Verfahren zur Herstellung von Phenol
US5518699A (en) Method of carrying out chemical reactions in reaction distillation columns
EP0506428B1 (de) Synthese von Methyl-t-butylether unter Verwendung von mit Sulfaten oder Schwefelsäure behandelten Oxiden der Gruppe IV
EP0037149A1 (de) Verfahren zur Herstellung von Aldehyden
US4338471A (en) Process for preparing phenol
US20100197978A1 (en) IPA From Propylene Using Mixed Metal Oxides
KR100567616B1 (ko) 고리형 지방족 옥심의 제조방법
US4894467A (en) Vapor phase oxidation or styrene to styrene oxide
US4754092A (en) Reducing methane production and increasing liquid yields in Fischer-Tropsch reactions
JPH0237895B2 (de)
US4247720A (en) Process for preparing -trimethylhydroquinone
US5210336A (en) Oxidation of olefin to glycol
JPS63248448A (ja) 触媒の製造方法およびオリゴマー化方法
US5106810A (en) Methanol dissociation catalysts
US4238371A (en) Methanation catalyst
CA1068727A (en) Ethynylation catalyst and process for producing alkynols
US4781862A (en) Process for the preparation of anthraquinone
EP0522666B1 (de) Verfahren zur Verringerung der Methanbildung und zur Steigerung der Ausbeute an flüssigen Produkten in einem Fischer-Tropsch-Verfahren

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19860820

17Q First examination report despatched

Effective date: 19870603

ITF It: translation for a ep patent filed

Owner name: FIAMMENGHI - DOMENIGHETTI

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

REF Corresponds to:

Ref document number: 3565977

Country of ref document: DE

Date of ref document: 19881208

ET Fr: translation filed
RAP4 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: SUMITOMO CHEMICAL COMPANY, LIMITED

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20031208

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20031211

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20031212

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20031215

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20050124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20050125

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

NLV7 Nl: ceased due to reaching the maximum lifetime of a patent

Effective date: 20050125